US3919183A - Perfluoroalkyl groups containing polymerisation products - Google Patents

Perfluoroalkyl groups containing polymerisation products Download PDF

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Publication number
US3919183A
US3919183A US397522A US39752273A US3919183A US 3919183 A US3919183 A US 3919183A US 397522 A US397522 A US 397522A US 39752273 A US39752273 A US 39752273A US 3919183 A US3919183 A US 3919183A
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formula
contain
polymerisation
recurring units
esters
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Horst Jager
Paul Schafer
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Novartis AG
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Ciba Geigy AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • C08F20/24—Esters containing halogen containing perhaloalkyl radicals

Definitions

  • ABSTRACT Polymerisation products of at least one perfluoroalkylalkyl ester of the formula The polymerisation products are useful for producing oleophobic, hydrophobic or dirt repellent finishes on various substrates.
  • the known homopolymers and copolymers produce useful oleophobic and hydrophobic effects, but the application amounts of the respective polymers are relatively large.
  • the present invention is based on the observation that it is possible to interrupt the perfluoroalkyl chains in the starting monomers by fluorine-free members, e.g. Cl-l, groups, without any impairment of the effect occurring with the application of the corresponding polymers, although the amount of fluorine responsible for the repellent effect is diminished.
  • the new polymerisation products are characterised by a very good repellent property in that they produce very good effects when used in very small amounts (as fluorine deposit on the fibre).
  • the present invention provides polymerisation products of at least one perfluoroalkylalkyl ester of the formula wherein R; represents an unbranched or branched perfluoroalkyl radical with 3 to 12 carbon atoms, R represents hydrogen or fluorine and R, and R, represent hydrogen or methyl and m is l or 2, n is a whole number from 2 to 12, and p is a whole number from 1 to 3, and optionally of other copolymerisable, ethylenically unsaturated monomeric compounds.
  • the polymerisation products can be homopolymers or copolymers.
  • the perfluoroalkyl radical in formula (1) can be an unbranched or a branched radical with 3 to [2, preferably 4 to 10, carbon atoms, and correspond approximately to the following formulae:
  • the copolymers contain recurring units of other ethylenically unsaturated copolymerisable compounds.
  • the number of recurring units can be about 10 to 400.
  • -molecular weight range is accordingly about 5000 to 230,000.
  • the manufacture of the starting monomers of the formula l) is carried out by known methods. These compounds are therefore obtained e. g. by reaction of the corresponding perfluoroalkylalkyl iodides with unsaturated monobasic acids or derivatives thereof in the presence of oleum or by reaction of the corresponding perfluoroalkylalkyl nitrates with the unsaturated acids in the presence of sulphuric acid. Suitable acids are e.g. acrylic, methacrylic, crotonic, and vinylacetic acids.
  • the polymerisation of the monomeric pertluoroalkylalkyl esters can take place in solution or in emulsion and in the presence of catalysts that liberate free radicals with themselves, with another perfluoroalkylallryl ester or with other compounds that can be polymerised to linear polymers.
  • vinyl esters of organic carboxylic acids e.g. vinyl acetate, vinyl formate, vinyl butyrate, vinyl benzoate,
  • vinyl alkyl ketones and vinyl alkyl ethers such as vinyl methyl ketone and vinyl butyl ether
  • vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride,
  • vinyl aryl compounds e.g. styrene and substituted styrenes
  • derivatives of the acrylic acid series e.g. acrylic nitrile or acrylic amide and preferably derivatives substituted at the amide nitrogen, e.g. N-methylolacrylamide, N-methylolacrylic amide alkyl ether, N,N-dihydroxyethylacrylic amide, N-tert.butyl-acrylic amide and hexametholylmelamine triacrylic amide, and the corresponding quaternised compounds,
  • esters of the acrylic acid series e.g. esters of acrylic acid, methacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, and monoor dialcohols containing from 1 to l8, preferably 8 to 12 carbon atoms, or phenols, e.g. ethyl acrylate, glycidyl acrylate, butylacrylate, acrylic acid monoglycol ester or dodecylacrylate, or N-dialkylaminoethylmethacrylate and the corresponding quatemised compound, and
  • polymerisable olefines such as isobutylene, butadiene or 2-chlorobutadiene
  • a is a whole number from 4 to 18, R, represents hydrogen or methyl, R represents hydrogen, methyl, or ethyl.
  • esters, amides or methylol amides of acrylic or methacrylic acid such as ethyl acrylate, hydroxyethyl acrylate and hydroxymethyl acrylate, butyl acrylate, glycidyl acrylate, glycolmonoacrylate, acrylic amide, methacrylate, methacrylic amide, N-methylolacrylic amide, N-methylolacrylic methyl ether, N-tert.butylacrylic amide
  • vinyl esters of organic carboxylic acids such as vinyl acetate
  • styrene vinyl halides, such as vinyl chloride or vinylidene chloride
  • polymerisable olefines such as isobutylene.
  • the polymers are composed as a rule of 5 to 100, preferably of 40 to 98, percent by weight of a perfluoroalkylalkyl ester and of 95 to 0, preferably 60 to 2, percent by weight of another compound.
  • Particular industrial importance attaches to those bi-, terand quaterpolymers that in addition to 40 to 98 percent by weight of the monomeric carboxylic acid perfluoroalkyl ester, based on the weight of the monomer, contain a reactive monomer, such as N-methylolacrylic amide, an acrylic ester, such as decylacrylate, and optionally a vinyl ester, such as vinyl acetate.
  • the manufacture of the polymers by homopolymerisation or copolymerisation of perfluoroalkylalkyl esters with one or more other copolymerisable ethylenically unsaturated monomers is carried out by conventional methods, for example by block polymerisation, bead polymerisation, polymerisation in aqueous emulsion or preferably by solvent polymerisation in a solvent suitable for this purpose, e.g. acetone, benzene, sym. di-
  • the polymerisation is effected advantageously with the application of heat, preferably to the boiling temperature of the solvent and accompanied by the addition of catalysts that form peroxidic or other free radicals and are soluble in the reaction medium, e.g. benzoyl peroxide, lauroyl peroxide, 01,01- azobisisobutyronitrile or potassium peroxide disulphate or redox systems, e.g. potassium peroxide disulphatelsodium bisulphite or ferrosulphate.
  • catalysts that form peroxidic or other free radicals and are soluble in the reaction medium
  • benzoyl peroxide lauroyl peroxide, 01,01- azobisisobutyronitrile
  • potassium peroxide disulphate or redox systems e.g. potassium peroxide disulphatelsodium bisulphite or ferrosulphate.
  • the polymeric compounds are obtained in the form of emulsions.
  • the polymerisation of the monomeric compounds in the presence of substrates.
  • it can be carried out on glass fibre fabrics or textile material.
  • the respective substrate is advantageously impregnated with solutions or emulsions of the monomers and subsequently the polymerisation is effected by addition of a polymerisation catalyst by heating the material.
  • the preferred polymerisation processes are emulsion polymerisation in an aqueous medium and solvent polymerisation.
  • the polymerisation is preferably carried out with a reaction time that is so adjusted that a virtually quantitative conversion of the monomer into the polymer is attached.
  • the maximum reaction time depends on the catalyst used and the polymerisation temperature and also on other conditions, but it is generally in the range from 0.5 to 24 hours.
  • the polymerisation temperature depends in turn on the chosen catalyst. In the case of emulsion polymerisation in aqueous medium it is in general in the range from 20 to 90C. Whereever possible, the polymerisation is carried out at atmospheric pressure.
  • the monomer(s) to be polymerised is (are) polymerised jointly in an aqueous solution of an emulsifier under nitrogen to a given monomer concentration of about 5 to about 50%. Normally the temperature is raised to 40 to C in order to effect the polymerisation in the presence of an added catalyst.
  • the concentration of the polymerisation catalyst is generally between 0.1 and 2%, based on the weight of the monomers.
  • Suitable emulsifiers are cationic, anionic, or nonionic surfactants.
  • the hydrophobic constituent of the emulsifier can be a hydrocarbon or fluorinated hydrocarbon.
  • Suitable cationic emulsifiers are for example quaternary ammonium salts, for example quaternary ammonium salts or amine salts that contain at least one longchain alkyl or fluoroalkyl group, or a benzene or naphthalene group that is highly substituted with alkyl to yield the hydrophobic constituent.
  • emulsifiers are the non-ionic surfactants in which the hydrophilic constituent is a poly(ethoxy) group and the hydrophobic constituent is either a hydrocarbon or a fluo rinated hydrocarbon group, e.g. the ethylene oxide condensates of alkylphenols, alkanols, alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylic acids, fiuoroalkylamides and the like.
  • Anionic emulsifiers are for example the sulphuric acid or phosphoric acid esters of the cited ethylene oxide condensates of long-chain alkylphenols, fatty a]- cohols, and fatty amines.
  • the monomer(s) is (are) dissolved in a suitable solvent, such as fluorinated solvents, for example hexafluoroxylene, benzotrifluoride, or mixtures thereof with acetone and/or ethyl acetate, and polymerised in a reaction vessel accompanied by the use of initiators such as azobisisobutyronitrile or other azo initiators, in concentrations of 0.1 to 2%, at 40 to 100C under nitrogen.
  • a suitable solvent such as fluorinated solvents, for example hexafluoroxylene, benzotrifluoride, or mixtures thereof with acetone and/or ethyl acetate
  • Preferred solvents are hexafluoroxylene, benztrifluoride, fluorine substituted halogenated hydrocarbons, other fluorinated solvents ans the like.
  • the polymerisation products are obtained in the form of solutions or dispersions that have a solids content of about to w pteferably to 25,.percent by weight. It is advantageous to use these solutions or dis persiohs diieet, optionally in dilute form, for the various applications.
  • the homopolymers or copolymers according to the invention can be used for treating porous or nonpon ous substrates, pfi'rfibly' rodudin g oleophobin, hydrophobic, or diet repellent sashes memes.
  • porous or nonpon ous substrates pfi'rfibly' rodudin g oleophobin, hydrophobic, or diet repellent sashes memes.
  • rous substrates there may be mentioned leadier and wood or especiallyiibre entertainments textiles and paper. Possible nonorous substrates are chiefly metal, plastic, and glass surfaces.
  • the compounds sceaiai" g to the invention can a be used for ex ple as aia namelysfdi as are lubricants for the prevention of est assesses-ten, of as tives for polish r
  • textiles made from wool, synthetic polyami'des, polyester, or polyaerylonitrile. Blended fabrics or blended knitted fabrics from cotton/polyester fibres can also be finished witli advantage.
  • the textiles can be in the form of threads, fibres, flocks, fleeces, but preferably of woven or knitted fabrics, and can be used for example as articles of clothing, upholstery materials, deco rating materials, and carpets.
  • Preparations that contain the polymeric perfluoro compounds can be applied to the substrate in known manner.
  • the substrates can be finished by being treated both with solutions, such as dispersions or emulsions, of the polymeric perfluoro compounds.
  • Fabrics can be impregnated e.g. by the exhaustion process or on a padder that is coated with the preparation at room temperature.
  • the impregnated material is then dried at 60 to 120C and subsequently optionally sunjected to a heat treatment at over 100C, e.g. from 120 to 200C, advantageously in the presence of known catalysts that donate acid.
  • Examples of further application methods are spraying, brushing, roll-coating, dusting with subsequent heat fixing or transfer of the polymers from an auxiliary material (paper, foil) accompanied by the application of heat.
  • the compounds according to the invention are applied in amounts of 0.1 to 10, preferably 0.5 to 5, percent by weight based on the substrate.
  • the polymers according to the invention it is also possible in particular to achieve soil-release and antisoiling effects on textile fibre substrates.
  • the copolymers are particularly suitable for this purpose.
  • EXAMPLE I a. A mixture of 30 parts of water, 0.6 part of dodecyltrimethylammonium chloride, 0.6 part of octadecyltrimethylammonium chloride, 0.4 part of vinyl acetate, 0.4 part of N-niethylolacrylic amide, 5 parts of acetone and 9.2 parts of the compound of the formula d FalA Ha zL 2 2 is heated with in a nitrogen atmosphere to C. A solution of 0.025 part of potassium peroxide disulphate in 2.5. parts iii water is added whereupon polymerisation occurs. Twenty minutes later a solution of 0.025 part of petassium peroxide disulphate in 2.5 parts of Water is aga' added.
  • the resulting emulsion is kept for 3 Boats at 70C to bring the polymerisation to completion.
  • Example 1(a) is a comparison example.
  • copolymers of the following fluorinated monomer compounds are manufactured according to the procedure 2(a):
  • the polymers from (6) and (f) are commercial products A llcation of the P01 mers
  • the monomer mixture contains (analysis by gas P y chromatography 1. Cotton fabric, polyester/cotton fabric (65/35), and
  • Homopolymers which contain about to 400 re- H l i curring units of the formula CHCHF Cmc"! T R1 i H R,(c11, F) (3,11,,0 -(CH,),, n wherein R has the meaning given in claim 2.
  • Copolymers which contain about 10 to 400 recurring units of the formula wherein R; represents an unbranched or branched per- 35 fluoroalkyl radical with 3 to 12 carbon atoms, I H
  • R represents hydrogen or fluorine
  • H R and R represents hydrogen or methyl and I i m is l or 2, v n a number g 2 m and 40 wherein R, represents an unbranched or branched perp a w o g number 1 m r fluoroalkyl radical with 3 to 12 carbon atoms, 2.
  • ftlgmopolymers accord ng to claim l, which con- R represents hydrogen or fluorine tain a ut 10 to 400 recumng units of the formula R1 and R2 represents hydrogen or methyl and m is l or 2,
  • n is a whole number from 2 to 12 and i 3 p is a whole number from 1 to 3, and up to 95% by CIFH P H weight of recurring units of at least one other ethylenically unsaturated monomer compound.
  • Copolymers according to claim 5 which contain about 10 to 400 recurring units of the formula wherein R represents hydrogen or fluorine and R and R represent hydrogen or methyl, n is a whole number from 4 to 10, and p is a whole number from 1 to 3. i H i 3.
  • Homopolymers according to claim 2, which con- -I -a+ H tain about 10 to 400 recurring units of the formula 1L,
  • R represents hydrogen or fluorine and R, and H I R, represent hydrogen or methyl
  • n is a whole number from 4 to 10
  • p is a whole number from I to 3.
  • Copolymers according to claim 6 which contain about 10 to 400 recurring units of theformula wherein R n and p have the meanings given in claim 3.
  • Copolymers according to claim 5 wherein as comonomers there are used members selected from the group consisting of esters, amides, methylol amides of acrylic or methacrylic acid, which optionally contain perfluoroalkyl groups, styrene, vinyl halides, vinylidene halides, vinyl esters of organic acids, and polymerisable olefines.
  • perfluoroalkylalkyl esters of the fonnula wherein R represents hydrogen or fluorine and R and R represent hydrogen or methyl, :1, is a whole number from 4 to 10, and p is a whole number from 1 to 3, are polymerised together with members selected from the group consisting of esters, amides, methylol amides of acrylic or methacrylic acid, which optionally contain perfluoroalkyl groups, styrene, vinyl halides and vinylidene halides, vinyl esters of organic acids, and polymerisable olefines.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
US397522A 1973-09-12 1973-09-17 Perfluoroalkyl groups containing polymerisation products Expired - Lifetime US3919183A (en)

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Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127711A (en) * 1977-03-31 1978-11-28 E. I. Du Pont De Nemours And Company Fluorine-containing terpolymers
US4303534A (en) * 1978-10-14 1981-12-01 Daikin Kogyo Co., Ltd. Foam fire-extinguishing composition and preparation and use thereof
US4351880A (en) * 1979-03-01 1982-09-28 Daikin Kogyo Co., Ltd. Prevention of adhesion of epoxy resins
US4563287A (en) * 1982-08-16 1986-01-07 Daikin Kogyo Co., Ltd. Aqueous fire-extinguishing composition
US4582882A (en) * 1982-10-13 1986-04-15 Minnesota Mining And Manufacturing Company Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith
US4590236A (en) * 1984-02-29 1986-05-20 Bayer Aktiengesellschaft Process for the production of hydrophobicizing and oleophobicizing agents
US4655807A (en) * 1983-11-29 1987-04-07 Daikin Kogyo Co., Ltd. Material for gas separating membrane
US4690869A (en) * 1984-03-09 1987-09-01 Daikin Kogyo Co., Ltd. Transparent coating material
US4728707A (en) * 1985-03-18 1988-03-01 Daikin Industries Ltd. Water- and oil-repellent
AU640758B2 (en) * 1990-03-29 1993-09-02 Mitsubishi Rayon Company Limited Fluoroacrylic polymer having lubricating effect and thermoplastic resin composition comprising same
US5608002A (en) * 1993-10-25 1997-03-04 Daikin Industries, Ltd. Water- and oil-repelling agent composition and process for preparing the same
US5879408A (en) * 1994-12-15 1999-03-09 Daikin Industries Ltd. Method of stainproofing cellulose fibers and stainproofed product
US6245854B1 (en) * 1998-12-11 2001-06-12 Visteon Global Technologies, Inc. Fluorocarbon-containing hydrophilic polymer coating composition for heat exchangers
US6353051B1 (en) 1999-03-10 2002-03-05 E. I. Du Pont De Nemours And Company Top coating for synthetic leathers
US6566470B2 (en) 2000-04-14 2003-05-20 Ciba Specialty Chemicals Corporation Fluorinated polymeric paper sizes and soil-release agents
US20030171497A1 (en) * 2002-02-15 2003-09-11 Simion Coca Thermosetting compositions containing alternating copolymers of isobutylene type monomers
US20050031885A1 (en) * 2002-02-15 2005-02-10 Martin Roxalana L. Waterborne thermosetting compositions containing alternating copolymers of isobutylene type monomers
US20050107536A1 (en) * 2002-12-20 2005-05-19 Shaffer Timothy D. Polymers with new sequence distributions
US20050148747A1 (en) * 2003-10-27 2005-07-07 Shobha Kantamneni Perfluoroalkyl substituted acrylate monomers and polymers thereof
US20060188729A1 (en) * 2005-02-22 2006-08-24 Kai-Volker Schubert Washable leather with repellency
US20060186368A1 (en) * 2005-02-22 2006-08-24 Liu Andrew H Leather treated with fluorochemicals
US7232872B2 (en) 2002-12-20 2007-06-19 Exxonmobil Chemical Patents Inc. Polymerization processes
US7414100B2 (en) 2004-06-21 2008-08-19 Exxonmobil Chemical Patents Inc. Polymerization process
US20080202384A1 (en) * 2007-02-28 2008-08-28 Sheng Peng Fluoropolymer compositions and method of use
US7425601B2 (en) 2002-12-20 2008-09-16 Exxonmobil Chemical Patents Inc. Polymers with new sequence distributions
US20090036706A1 (en) * 2006-03-10 2009-02-05 Unimatec Co., Ltd. Polyfluoroalkyl Alcohol, Or (METH)Acrylic Acid Derivative Thereof, And Process For Producing The Same
US7662892B2 (en) 2004-06-21 2010-02-16 Exxonmobil Chemical Patents Inc. Impact copolymers
US7723447B2 (en) 2002-12-20 2010-05-25 Exxonmobil Chemical Patents Inc. Polymerization processes
US7799882B2 (en) 2005-06-20 2010-09-21 Exxonmobil Chemical Patents Inc. Polymerization process
US7858736B2 (en) 2004-06-21 2010-12-28 Exxonmobil Chemical Patents Inc. Polymer recovery method
US20110009555A1 (en) * 2007-09-10 2011-01-13 Unimatec Co., Ltd. Fluorine-containing polymer and surface-modifying agent containing the same as active ingredient
US7981984B2 (en) 2004-06-21 2011-07-19 Exxonmobil Chemical Patents Inc. Polymerization process
US20110178260A1 (en) * 2010-01-20 2011-07-21 Sheng Peng Fluoropolymer compositions and method of use
US20120094020A1 (en) * 2004-03-26 2012-04-19 Florida State University Research Foundation, Inc. Hydrophobic fluorinated polyelectrolyte complex films and associated methods

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EP0484462B1 (en) * 1989-07-24 1995-11-15 Gelman Sciences, Inc. Process for treating a porous substrate to achieve improved water and oil repellency
US5288825A (en) * 1990-03-29 1994-02-22 Mitsubishi Rayon Company Ltd. Fluoroacrylic polymer having lubricating effect and thermoplastic resin composition comprising same
WO1995011877A1 (fr) * 1993-10-27 1995-05-04 Elf Atochem S.A. Alcools polyfluores et leurs procedes de preparation
JP5541272B2 (ja) * 2011-12-12 2014-07-09 ユニマテック株式会社 含フッ素共重合体およびそれを有効成分とする撥水撥油剤
CN107513127A (zh) * 2016-06-17 2017-12-26 默克专利股份有限公司 含氟聚合物

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Patent Citations (2)

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US3457247A (en) * 1965-02-12 1969-07-22 Daikin Ind Ltd Fluorocarbon compounds and polymers thereof

Cited By (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127711A (en) * 1977-03-31 1978-11-28 E. I. Du Pont De Nemours And Company Fluorine-containing terpolymers
US4303534A (en) * 1978-10-14 1981-12-01 Daikin Kogyo Co., Ltd. Foam fire-extinguishing composition and preparation and use thereof
US4351880A (en) * 1979-03-01 1982-09-28 Daikin Kogyo Co., Ltd. Prevention of adhesion of epoxy resins
US4563287A (en) * 1982-08-16 1986-01-07 Daikin Kogyo Co., Ltd. Aqueous fire-extinguishing composition
US4582882A (en) * 1982-10-13 1986-04-15 Minnesota Mining And Manufacturing Company Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith
US4655807A (en) * 1983-11-29 1987-04-07 Daikin Kogyo Co., Ltd. Material for gas separating membrane
US4590236A (en) * 1984-02-29 1986-05-20 Bayer Aktiengesellschaft Process for the production of hydrophobicizing and oleophobicizing agents
US4690869A (en) * 1984-03-09 1987-09-01 Daikin Kogyo Co., Ltd. Transparent coating material
US4728707A (en) * 1985-03-18 1988-03-01 Daikin Industries Ltd. Water- and oil-repellent
AU640758B2 (en) * 1990-03-29 1993-09-02 Mitsubishi Rayon Company Limited Fluoroacrylic polymer having lubricating effect and thermoplastic resin composition comprising same
US5608002A (en) * 1993-10-25 1997-03-04 Daikin Industries, Ltd. Water- and oil-repelling agent composition and process for preparing the same
US5879408A (en) * 1994-12-15 1999-03-09 Daikin Industries Ltd. Method of stainproofing cellulose fibers and stainproofed product
US6245854B1 (en) * 1998-12-11 2001-06-12 Visteon Global Technologies, Inc. Fluorocarbon-containing hydrophilic polymer coating composition for heat exchangers
US6353051B1 (en) 1999-03-10 2002-03-05 E. I. Du Pont De Nemours And Company Top coating for synthetic leathers
US6818717B2 (en) 2000-04-14 2004-11-16 Ciba Specialty Chemicals Corporation Fluorinated polymeric paper sizes and soil-release agents
US6566470B2 (en) 2000-04-14 2003-05-20 Ciba Specialty Chemicals Corporation Fluorinated polymeric paper sizes and soil-release agents
US20040082745A1 (en) * 2000-04-14 2004-04-29 Shobha Kantamneni Fluorinated polymeric paper sizes and soil-release agents
US20040242777A1 (en) * 2002-02-15 2004-12-02 Simion Coca Thermosetting compositions containing alternating copolymers of isobutylene type monomers
US6784248B2 (en) * 2002-02-15 2004-08-31 Ppg Industries Ohio, Inc. Thermosetting compositions containing alternating copolymers of isobutylene type monomers
US20030171497A1 (en) * 2002-02-15 2003-09-11 Simion Coca Thermosetting compositions containing alternating copolymers of isobutylene type monomers
US20040249075A1 (en) * 2002-02-15 2004-12-09 Rechenberg Karen S. Powder coating compositions having improved mar and acid resistance
US20050031885A1 (en) * 2002-02-15 2005-02-10 Martin Roxalana L. Waterborne thermosetting compositions containing alternating copolymers of isobutylene type monomers
US7122600B2 (en) 2002-02-15 2006-10-17 Ppg Industries Ohio, Inc. Powder coating compositions having improved mar and acid resistance
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JPS5055689A (enrdf_load_stackoverflow) 1975-05-15
CA1024698A (en) 1978-01-17
GB1433908A (en) 1976-04-28
CH582719A5 (enrdf_load_stackoverflow) 1976-12-15
SU508214A3 (ru) 1976-03-25
FR2243209A1 (enrdf_load_stackoverflow) 1975-04-04
JPS532187B2 (enrdf_load_stackoverflow) 1978-01-26

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